CN103305145A - Primerless removable adhesive systems - Google Patents
Primerless removable adhesive systems Download PDFInfo
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- CN103305145A CN103305145A CN2013100750840A CN201310075084A CN103305145A CN 103305145 A CN103305145 A CN 103305145A CN 2013100750840 A CN2013100750840 A CN 2013100750840A CN 201310075084 A CN201310075084 A CN 201310075084A CN 103305145 A CN103305145 A CN 103305145A
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- label
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- polymkeric substance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2425/00—Presence of styrenic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249962—Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
Abstract
This invention relates to a primerless removable or repositionable pressure sensitive tape or label comprises a porous substrate material, and a pressure sensitive adhesive (PSA) composition comprising (i) 10 to 90 wt.%, based on the combined weight of parts (i) and (ii), of one or more aqueous adhesive (co)polymer, and (ii) 90 to 10 wt.%, based on the combined weight of parts (i) and (ii), of one of more water-dispersed thermoplastic material, wherein the water-dispersed thermoplastic material is incompatible with the aqueous adhesive (co)polymer.
Description
Invention field
The present invention relates to Pressure Sensitive Tape or label without priming paint, it comprises porous substrates material and pressure sensitive adhesive (PSA) composition, said composition comprises following component (i) and (ii), namely (i) is take component (i) and gross weight (ii) as benchmark, one or more aqueous binders (copolymerization) polymkeric substance of 10-90 % by weight, (ii) take component (i) and gross weight (ii) as benchmark, the thermoplastic material of one or more water-dispersions of 90-10 % by weight, the wherein thermoplastic material of this water-dispersion and this aqueous binder (copolymerization) polymkeric substance incompatible (incompatible).The present invention can be the form of the paper label made by the PSA composition.Band of the present invention and label can be removed maybe and can reappose.
Technical background
Removable tackiness agent is used for many special bands and tag application just more and more.If can remove band or label construction in the situation that surface layer (facestock) inefficacy does not occur, if perhaps after removing, do not stay obvious resistates, then tackiness agent can be called removable tackiness agent.These tackiness agents comprise multiple different chemical substance and carrier.Since exist various application conditions, used surface layer, with and the final application substrate that applies, so need many different performance curves.
Because people design the level of adhesion of these materials very low, so may be a problem with the stationarity (or binding property) of surface layer.By overcoming with primer coating, described primer coating can increase cost and the complicacy of structure usually for this.Can buy the surface layer that some use the coating bottoming of higher-energy in advance.In the time of many, primer coating and dry on surface layer, described prime coat and adhesive coating mixed production (in-line), perhaps applying as the independent operation on the coating equipment prime coat.Some the most effective priming paint are permanent PSA; But this mode has increased extra layer, more complicated.If priming paint is very sticking, then can't repeat to twine with self canoe.The mode of another kind of priming is to apply non-pressure sensitive at surface layer, and this surface layer has special specific adhesion to removable tackiness agent.When priming paint must apply with independent operation and on priming paint arranged surface layer before application of adhesive when repeating to twine state, this is the way of usually taking.These materials normally chemical property are very similar to the material of tackiness agent.In addition, when priming paint was put on porous friction course with fluid state, this priming paint can flow in the surface layer to a certain extent, when this priming paint solidifies, can form because tangle very strong bonding.Therefore improved stationarity.In a word, when promoting binding property with surface layer with priming paint, the cost of system and complicacy can be affected.
By to have priming paint and not the tackiness agent that applies of the panel of priming check the resistates that stainless steel plate stays after peeling off test, can estimate the validity that can remove tackiness agent.Can carry out thermal ageing (50 ℃ of for example carrying out for 1 week before peeling off are aging) so that more fully data to be provided to sample.Under these conditions, to on have priming paint and not the system of priming compare, the system of priming does not show a large amount of adhesive residue at stainless steel plate, shows that tackiness agent to its substrate that applies obvious transfer has occured from the design retention position on the surface layer.Substantially there is not to have on the adhesive residue proof removability of the system of priming paint on the plate.
Further specify the necessity of priming, on stainless steel substrate, with the different time two kinds of tackiness agents are worn out.Even the transfer to substrate all can occur, no matter and the length of the residence time in the tackiness agent for low separability and higher separability.By as seen from Table 1, priming is to improve fixed a kind of effective means.
Priming paint and 90 ° of stainless steel separabilities of the tackiness agent of priming (ounce/inch) are not arranged on the table 1.
The A=adhesive failure, AFB=from the adhesive failure of backing.
When the surface layer of paying close attention to was vesicular, for example the paper layer if tackiness agent can flow in the hole, then only needed single to apply the stationarity that tackiness agent just can be realized improvement.Removable tackiness agent has very high adhesion strength and less cold flow properties (cold flow) usually, therefore when it being shifted coating, only has very small amount of tackiness agent to flow in the hole.A kind of method of alleviating this problem is to be added in can flow to when applying in the hole but the material that has very little cold flow properties under final application conditions.The crystalline material that has thermoplasticity or show to a certain degree has following potentiality, namely presents when molten state than low viscosity but show rigidity when vitreous state or crystal form.Because most of PSA need heating when applying, so can find the material of experience phase transformation, occur between the described phase transformation temperature that reticulation reaches in coating procedure and the envrionment conditions temperature.In addition, if will keep this required phenomenon, wish very that then this material can remain the phase that is independent of tackiness agent body phase.
Will study in more detail this phenomenon, preparation comprises and does not comprise the sample of thermoplastic filler (35 % by weight), makes the duplexer transmission by hot roller nip, sample is shifted being coated on the paper.Then by low temperature cutting preparation cross section, take the surface by scanning electronic microscope.Because filler is the low viscosity material of easier melting by roll gap the time, so filler more easily flows in the hole of paper.In microphotograph, to compare with the system that does not contain thermoplastic filler, this difference looks and resembles more coarse interface.Other test shows owing to having added filler, stationarity be improved significantly.
Have constantly held, by add wax in tackiness agent, the PSA preparation just can be realized this effect; For example referring to No. the 5073457th, the United States Patent (USP) (transferring 3M company) of Blackwell.Blackwell proposes petroleum wax (paraffin or polyethylene or polypropylene are emulsions) and solvent-based or water base acrylic adhesives blending.In the Blackwell document, used the wax of low amount, the document has been described the stationarity of improving, and thinks that itself and wax flow in the hole of substrate relevant.Wax has low surface energy and low viscosity under the melting form.Therefore, the wax that can add the low levels level reduces binding property, because from thermodynamics, wax should be activated and shift to surperficial.This also can limit the amount that can flow to the material in the substrate hole, because the wax of high level level may flood adhesive surface to a certain extent, thereby loses too much binding property.
The present invention has made removed PSA system without priming paint with the effective simple method of cost, and it further provides the balance between the adhesion integrity and gained system bond properties in the system of improving.Use can further provide more controlled system with these character of balance based on the tackifier of C5 or other suitable thermoplastic filler.
Summary of the invention
Of the present inventionly comprise porous substrates material and pressure sensitive adhesive (PSA) composition without priming paint Pressure Sensitive Tape or label, said composition comprises following component (i) and (ii), that is: (i) is take component (i) and gross weight (ii) as benchmark, one or more aqueous binders (copolymerization) polymkeric substance of 10-90 % by weight, (ii) take component (i) and gross weight (ii) as benchmark, the thermoplastic material of one or more water-dispersions of 90-10 % by weight, wherein the thermoplastic material of this water-dispersion and aqueous binder (copolymerization) polymkeric substance is incompatible.The present invention can be the form of the paper label made by the PSA composition.Band of the present invention and label can be removed maybe and can reappose.
Porous substrates without priming paint Pressure Sensitive Tape or label can comprise paper.Aqueous binder multipolymer without priming paint Pressure Sensitive Tape or label can comprise acrylic acid or the like (copolymerization) polymkeric substance, and the thermoplastic material of water-dispersion can be selected from lower group: based on tackifier, styrene block copolymer, ethylene vinyl acetate copolymer, ethylene acrylic copolymer and olefines (copolymerization) polymkeric substance of C5.The thermoplastic material that preferably water is disperseed comprises that one or more are based on the tackifier of C5.
Aqueous binder (copolymerization) polymkeric substance can have and is equal to or less than 0 ℃ Tg, can be formed by one or more ethylenically unsaturated monomers.The monomer that is used to form aqueous binder can be selected from lower group: (methyl) acrylic acid (C
1-C
20) alkyl or (C
3-C
20) alkenyl esters, and combination.Also can comprise the component that one or more are selected from lower group without priming paint Pressure Sensitive Tape or label: tensio-active agent, rheology modifier, linking agent, defoamer, softening agent, non-tackifier based on C5, pigment and stablizer.
Detailed Description Of The Invention
Of the present inventionly comprise porous substrates material and pressure sensitive adhesive (PSA) composition without priming paint Pressure Sensitive Tape or label, said composition comprises following component (i) and (ii), that is: (i) is take component (i) and gross weight (ii) as benchmark, one or more aqueous binders (copolymerization) polymkeric substance of 10-90 % by weight, (ii) take component (i) and gross weight (ii) as benchmark, the thermoplastic material of one or more water-dispersions of 90-10 % by weight, wherein the thermoplastic material of this water-dispersion and aqueous binder (copolymerization) polymkeric substance is incompatible.The present invention is the form of the paper label made by the PSA composition.Band of the present invention and label can be removed maybe and can reappose.
The PSA that is applicable in bottomless varnish-treated tape or the label can comprise that blending has water soluble acrylic acid ester adhesive (copolymerization) polymkeric substance of the thermoplastic material of water-dispersion.The binder polymer that term " acrylate " expression forms with the monomer based on (methyl) vinylformic acid and (methyl) acrylate that is equal to or greater than 50%.Water-based PSA(copolymerization) polymkeric substance can have following Tg, and it is equal to or less than 0 ℃, perhaps is equal to or less than-20 ℃, perhaps in-20 ℃ to-60 ℃ scope, perhaps in-20 ℃ to-65 ℃ scope.
Can come polymerization water-based PSA(copolymerization with in the multiple ethylenically unsaturated monomers one or more) polymkeric substance.The example that is applicable to form single ethylenically unsaturated monomers of water-based PSA comprises (methyl) acrylic acid various (C
1-C
20) alkyl or (C
3-C
20) alkenyl esters, comprise methyl acrylate (MA), methyl methacrylate (MMA), (methyl) ethyl propenoate (EA and EMA), (methyl) butyl acrylate (BA and BMA), (methyl) vinylformic acid 2-hydroxyl ethyl ester (HEA and HEMA), (methyl) 2-EHA (EHA and EHMA), (methyl) benzyl acrylate, (methyl) lauryl acrylate, (methyl) vinylformic acid grease, (methyl) vinylformic acid palm ester and (methyl) stearyl acrylate ester; The example that is applicable to form single ethylenically unsaturated monomers of water-based PSA also comprises vinylbenzene, Vinyl toluene, ethene, vinyl-acetic ester, vinylchlorid, vinylidene chloride, vinyl cyanide, (methyl) acrylamide.In this manual, used term " (methyl) " before another term, for example the situation in (methyl) acrylate and (methyl) acrylamide represents respectively acrylate or methacrylic ester and acrylamide or Methacrylamide.
Water-based PSA(copolymerization) polymkeric substance also can be formed by the monomer of other types.For example, PSA can be the combination of styrene-butadiene-rubber (SBR) composition, natural rubber (NR) composition, olefin block copolymers (OBC) composition or these materials and aforesaid propylene acid esters (copolymerization) polymkeric substance.
Prepare to be selected from lower group with the water dispersible thermoplastic material of water base PSA blending: based on tackifier, styrene block copolymer, ethylene vinyl acetate copolymer, ethylene acrylic copolymer and alkene (copolymerization) polymkeric substance or its combination of C5.Represent the material that the C5 distillation stage (cut) by petroleum refinement technique obtains, for example m-pentadiene based on the tackifier of C5.These comprise the isomer of amylene and pentadiene usually.They can be straight chain, side chain or ring-type or its combination.Based on the weight-average molecular weight of the tackifier of C5 usually less than 10000.The suitable commercially available TACOLYN5193 that obtains from Yisiman Chemical Company's (Tennessee State Ke Yinsi baud) (Eastman Chemical Company, Kingsport, TN) of including, but are not limited to based on the C5 tackifier.In the situation based on the tackifier resins of C5 and PSA polymer-compatible, those skilled in the art can easily find other non-compatible resins as the water dispersible thermoplastic material.Referring to " the compatibility of natural rubber and tackifier such as people such as M.Fujita.I. the phasor of the blend of natural rubber and rosin and terpine resin (Miscibility between Natural Rubber and Tackifiers.I.Phase Diagrams of the Blends of Natural Rubber with Rosin and Terpene Resins) "; applied polymer science periodical (Journal of Applied Polymer Science); the 64th volume; o. 11th; 2191-2197 page or leaf (on June 13rd, 1997), the document has been described the rosin tackifier with the inconsistent polymerization of natural rubber.
The water dispersible thermoplastic material can be hydrocarbon (copolymerization) polymkeric substance, and it includes, but are not limited to the BlueWave according to Dow Chemical (Dow Chemical Company)
TMThe olefines that mechanical dispersion process makes (copolymerization) polymkeric substance.An example of this material is the HYPOD from Dow Chemical (available) (Midland, MI)
TM8501 dispersions.
Take the gross weight of binder polymer and thermoplastic material as benchmark, the level that exists of water dispersible thermoplastic material is the 10-90 % by weight, or the 10-40 % by weight, or the 25-35 % by weight.The binder polymer that can have magnitude of recruitment, take the gross weight of binder polymer and thermoplastic material as benchmark, there is level in it is the 90-10 % by weight, or the 60-90 % by weight, or the 65-75 % by weight.
The material that is applicable to thermoplastic material includes, but are not limited to and the inconsistent any thermoplastic material of tackiness agent itself; That is, the material of interpolation forms two kinds of different phases from the blending of tackiness agent (copolymerization) polymkeric substance the time, have separately himself second-order transition temperature (Tg) or temperature of fusion (Tm).Non-compatibility or incompatible material are not the material mixing with molecular level and its adding.If tackiness agent is acrylic acid or the like (copolymerization) polymkeric substance, then suitable thermoplastic filler material comprises inconsistent tackifier (for example based on C5 tackifier), styrene block copolymer, ethylene vinyl acetate copolymer, ethylene acrylic copolymer and olefin polymer.The water-dispersible material that is applicable among the water base PSA has greater than 10 at 25 ℃
7The modulus of dynes per centimeter has less than 10 at 150 ℃
4The modulus of dynes per centimeter.
For the non-acrylate tackiness agent, those skilled in the art can select suitable thermoplastic material.High-molecular weight polymer is usually incompatible mutually.Some feature of material can instruct appropriate selection and avoid disadvantageous combination.For example, if other additives all are compatible in thermoplastic material and polymkeric substance such as tackifier, softening agent or oil, preparation are become be difficult to operation.In addition, if tackiness agent all has common mutually (for example ethene) with thermoplastic material, then can go wrong aspect the interaction of phase, again cause being difficult to operate preparation.
Those skilled in the art can easily find mutual incompatible polymers.Although many monomers can both be dissolved in the various polymkeric substance, when these monomer polymerizations, solubleness can obviously reduce along with extent of polymerization.For example, in the situation of natural rubber latex, those skilled in the art can easily find mutually inconsistent acrylic acid or the like (copolymerization) polymkeric substance or ethylene vinyl acetate (EVA) (copolymerization) polymkeric substance.For styrene butadiene latices, can easily find acrylic acid or the like or the EVA(copolymerization that can form second-phase (that is, incompatible)) polymkeric substance.
The molecular weight of binder polymer will depend on selected chemical property.In general, for unblocked polymkeric substance, most of acrylate (copolymerization) polymkeric substance for example, weight-average molecular weight will be above 100000amu.The molecular weight of thermoplastic material can be low to moderate approximately 1000amu usually less than 100000amu.
By PSA composition (comprising thermoplastic material and other components) is coated on the porous substrates material, form Pressure Sensitive Tape or label without priming paint.A kind of method for preparing band or label construction is with PSA composition drop-down (draw down) (for example dried coating level is 0.8 mil) to the silicone release liner, then the PSA composition layer is transferred to required porous substrates from release liner.In this method, wish the temperature that raises (for example temperature be equal to or higher than 60 ℃ or be equal to or higher than 80 ℃ or be equal to or higher than 100 ℃ or be 60-120 ℃) under, be equal to or higher than under the temperature of the temperature of fusion (Tm) of thermoplastic material or second-order transition temperature (Tg) the PSA composition carried out transfer step.Perhaps, can select thermoplastic material, so that it is in when heating fusing and have the setting time of prolongation; That is, thermoplastic polymer can be cooled to certain temperature, below the temperature, polymkeric substance will solidify at this, and when this temperature, polymkeric substance will keep melting within the time that prolongs.Some thermoplastic polymer can have long " open hour ", and the crystalline polymer for carrying out deepfreeze after the fusing in baking oven can cause this situation.This may be favourable, because when tackiness agent leaves baking oven, so just has more times to be used for it is transferred to the paper layer.For example, for based on the EVA(copolymerization) preparation of polymkeric substance, this phenomenon is well-known.
Do not wish to be subject to the restriction of any theory, the contriver be sure of, makes composition be in molten state (adopting or do not adopt the temperature of rising) and is conducive to fixed effect in the hole that thermoplastic material moves to porous substrates.The PSA composition can be in when contacting with porous substrates under the suitable rising temperature.In the method for using release liner, so that the duplexer of release liner/PSA composition/porous substrates passes through just enough with suitable temperature and linear velocity between warming mill.One set condition can be 105 ℃ temperature and 10 m/mins linear velocity.Other modes that realize coating step are well known in the art.
The porous substrates that is used to form without priming paint Pressure Sensitive Tape or label can be paper, fabric or complex body or reticulation.Substrate can be through applying or uncoated, and prerequisite is that the material that obtains keeps enough porositys.Paper can comprise such as other materials such as hard papers.
The PSA that is used to form without priming paint Pressure Sensitive Tape or label also can comprise the component that one or more are selected from lower group: tensio-active agent, rheology modifier, linking agent, defoamer, softening agent, non-based on C5 tackifier, pigment and stablizer (for example UV stabilizer, antioxidant).
Dow Chemical can be by having used its BlueWave
TMTechnological Economy saving ground dispersed polymer weight polymers (referring to " chemistry and engineering communication (Chemical and Engineering News) ", 84(49), the 40th page (2006)).This is the patented method that a kind of mechanical dispersion higher molecular weight polymer realizes hanging down particle diameter simultaneously.Therefore, now can prepare many thermoplastic materials as dispersion, and former these right and wrong are commercially available.Owing to having obtained the more material of wide region, can also need to regulate finished-product material for using better.
Some steps of in shifting coating procedure, carrying out have been considered.At first, coated materials is on release liner, dry in baking oven, after it is taken out from baking oven, pass through at once roll gap, thereby it is transferred to surface layer.In some cases, make gauze (paper web) again wetting, thereby reduce as far as possible curling.In other words, so that reticulation as far as possible at once cooling after leaving baking oven.Therefore, it all is favourable prolonging any preparation of the open hour of molten charge material.The present invention has realized the purpose of longer open hour, so that thermoplastic material has the more time to be used to permeate substrate and strengthens fixing.This thermoplastic material that can not solidify at once by selecting can be cooled to be lower than its fusing point is realized.An example is HYPOD8501(Dow Chemical, available).
Of the present invention can be used for forming without priming paint Pressure Sensitive Tape or label have paper substrate band and the label that can remove the character that maybe can reappose.These bands and label can be formed by the surface layer beyond the paper, and prerequisite is that this surface layer has suitable porosity.Gained band or label can be used as Masking strip, printer color tape, label, removable sticky note book and other have benefited from the application of removability.
Can easily follow the tracks of phase transformation by dsc (DSC), this is a kind of technology of monitoring hot-fluid in the temperature that raises gradually with controllable rate.Can infer from the thermogram with water-based acrylate (copolymerization) polymkeric substance of the wax preparation that disperses, in approximately 80 ℃ of phase transformations that detect wax, and temperature of fusion and recrystallization temperature only differ the several years.This shows, wax can snap cure when cooling.
By carefully selecting the raw material of thermoplastic material, can reduce recrystallization temperature, thus the open hour when prolonging its cooling.For example consider the situation of the polyethylene polymer of dispersion.Utilize DSC to obtain thermogram with the water-based acrylate PSA of the polyolefin dispersion of 30 % by weight preparation.Equally, phase transformation is higher than envrionment conditions.But in this case, fusing is finished the temperature head that begins with recrystallization and is about 30 ℃.Under 10 ℃/minute rate of cooling condition, this was corresponding to 3 minutes of real-time conditions.Because the time of advancing by baking oven and nip point for duplexer only is several seconds, so that this species diversity will become in commercial applications will be larger.
Embodiment
Two kinds of tackiness agent (ROBOND of two kinds of fillers (TACOLYN5193 and HYPOD8501) preparation with various contents levels
TMPS-8931 and ROBOND PS-8120HV(Dow Chemical, available)), as substituting the paper priming.For the priming paint sample, binding agent P-376 is coated on the 60#Krome paper.Adhesive sample shifted being coated to Krome paper from Chemsultants RP-12 release liner, and in 80 ℃ of baking ovens dry 5 minutes.In order to promote failure mode to be varied to binding property the bonding test process from AFB, make sample after drop-down with the speed of about 12 feet per minute clocks (the approximately 4 m/mins) laminating machine by 225 °F (108 ℃).
At the appointed time (20 minutes, 1 day and 1 week) sample that remains on the PSTC ambient test conditions is peeled off test.In order to accelerate aging and accumulative effect is peeled off in reinforcement, sample was placed for 1 week in 50 ℃ of baking ovens.Measure 180 ° of separabilities with PSTC testing method 101.
Table 2. separability and peel off accumulation
The A=adhesive failure, PT=paper is torn, and the adhesive failure (from the tackiness agent of backing) that M=mixes and adhesion (cohesive) were lost efficacy
Adding hard thermoplastic filler material can reduce the separability of tackiness agent, therefore also comprises the tackiness agent of low separability in contrast.Clearly, the sample that has added filler all shows good removability under all residence time.
By the finger friction testing stationarity is finally measured (carrying out qualitative grading with the surface of pointing back and forth frictional adhesion agent and to stationarity).
Table 3. finger friction testing
1=is poor splendid to 5=
Equally, comprise the PSA composition of the blend of water-based acrylate PSA and water dispersible uncompatibility thermoplastic filler material by use, detect the stationarity of obvious improvement.
Table 4. filler content level
The A=adhesive failure, PT=paper is torn, and the adhesive failure that M=mixes and adhesion were lost efficacy.
Add the water dispersible thermoplastic filler material of uncompatibility to preparation, can obtain integral type from the tackiness agent of bottoming.This preparation can be cancelled some steps in the manufacturing process, thereby reduces cost and complicacy.In addition, at present in dispersion technology, improve that the thermoplastic material of broad range can be used among the water base PSA so that have more.Therefore, can optimize better for final application conditions target the thermal properties of any thermoplastic material phase.
Claims (7)
1. Pressure Sensitive Tape or label without a priming paint, described Pressure Sensitive Tape or label comprise:
A) porous substrates material, and
B) PSA composition, described PSA composition comprises:
I) take component (i) and gross weight (ii) as benchmark, one or more aqueous binders (copolymerization) polymkeric substance of 10-90 % by weight, and
Ii) take component (i) and gross weight (ii) as benchmark, the thermoplastic material of one or more water-dispersions of 10-90 % by weight, the thermoplastic material of wherein said water-dispersion is incompatible with described aqueous binder (copolymerization) polymkeric substance.
2. as claimed in claim 1ly it is characterized in that without priming paint Pressure Sensitive Tape or label, described porous substrates material comprises paper.
3. as claimed in claim 1 without priming paint Pressure Sensitive Tape or label, it is characterized in that, described aqueous binder (copolymerization) polymkeric substance is acrylate (copolymerization) polymkeric substance, and the thermoplastic material of described water-dispersion is selected from lower group: based on tackifier, styrene block copolymer, ethylene vinyl acetate copolymer, ethylene acrylic copolymer and olefines (copolymerization) polymkeric substance of C5.
4. as claimed in claim 3ly it is characterized in that without priming paint Pressure Sensitive Tape or label, the thermoplastic material of described water-dispersion comprises one or more based on the tackifier of C5.
5. as claimed in claim 1ly it is characterized in that without priming paint Pressure Sensitive Tape or label, described aqueous binder (copolymerization) polymkeric substance has and is equal to or less than 0 ℃ Tg, is formed by one or more ethylenically unsaturated monomers.
6. as claimed in claim 1ly it is characterized in that without priming paint Pressure Sensitive Tape or label, at least 50% the monomer that polymerization forms described aqueous binder is selected from lower group: (methyl) acrylic acid (C
1-C
20) alkyl or (C
3-C
20) alkenyl esters, and combination.
7. as claimed in claim 1 without priming paint Pressure Sensitive Tape or label, it is characterized in that, described band or label also comprise one or more components that is selected from lower group: tensio-active agent, rheology modifier, linking agent, defoamer, softening agent, non-tackifier based on C5, pigment and stablizer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261608731P | 2012-03-09 | 2012-03-09 | |
| US61/608,731 | 2012-03-09 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103305145A true CN103305145A (en) | 2013-09-18 |
| CN103305145B CN103305145B (en) | 2015-11-18 |
Family
ID=47757474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310075084.0A Active CN103305145B (en) | 2012-03-09 | 2013-03-08 | Without the removed adhesive composition of priming paint |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US9163165B2 (en) |
| EP (1) | EP2636713B1 (en) |
| CN (1) | CN103305145B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104021728A (en) * | 2014-06-24 | 2014-09-03 | 成都市天星印务有限公司 | Novel material formula of high-strength adhesive and fragile paper label thereof |
| CN108611026A (en) * | 2018-04-28 | 2018-10-02 | 王锦云 | A kind of aqueous EVA adhesive and preparation method thereof |
| CN110582548A (en) * | 2017-03-13 | 2019-12-17 | 陶氏环球技术有限责任公司 | Water-based pressure-sensitive adhesive composition and method for producing the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11066576B2 (en) | 2015-09-21 | 2021-07-20 | United States Gypsum Company | Drywall joint tape with dual purpose adhesive backing |
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| CN1205733A (en) * | 1995-12-22 | 1999-01-20 | 美国3M公司 | Blended pressure-sensitive adhesives |
| EP0913443A1 (en) * | 1996-07-19 | 1999-05-06 | Toagosei Co., Ltd. | Heat-sensitive and pressure-sensitive adhesive sheet |
| CN1333804A (en) * | 1998-12-15 | 2002-01-30 | 艾弗里·丹尼森公司 | Removable emulsion pressure-sensitive adhesives |
| EP1318180A1 (en) * | 2001-12-06 | 2003-06-11 | Permacel | Aqueous pressure-sensitive adhesive composition, production method therefor and pressure-sensitive adhesive tape using the composition |
| CN100999650A (en) * | 2006-01-13 | 2007-07-18 | 日东电工株式会社 | Aqueous pressure-sensitive adhesive composition, pressure-sensitive adhesive tape and wire harness |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5073457A (en) | 1988-12-01 | 1991-12-17 | Minnesota Mining And Manufacturing Company | Repositionable adhesive |
| DE4432368A1 (en) | 1994-09-12 | 1996-03-14 | Lohmann Gmbh & Co Kg | Water-soluble pressure-sensitive adhesive with high temp. shear strength |
| US5925432A (en) | 1994-09-16 | 1999-07-20 | Avery Dennison Corporation | Primerless pressure-sensitive adhesive constructions |
| NZ316689A (en) | 1995-12-22 | 1999-04-29 | Minnesota Mining & Mfg | Blended pressure-sensitive adhesives comprising two components, one being pressure sensitive and the other being a thermoplastic material |
| RU2525904C2 (en) * | 2008-07-02 | 2014-08-20 | ЗМ Инновейтив Пропертиз Компани (ЗМ Innovative Properties Company) | Low-surface energy adhesive |
-
2013
- 2013-02-20 US US13/771,192 patent/US9163165B2/en active Active
- 2013-02-28 EP EP13157313.1A patent/EP2636713B1/en active Active
- 2013-03-08 CN CN201310075084.0A patent/CN103305145B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205733A (en) * | 1995-12-22 | 1999-01-20 | 美国3M公司 | Blended pressure-sensitive adhesives |
| EP0913443A1 (en) * | 1996-07-19 | 1999-05-06 | Toagosei Co., Ltd. | Heat-sensitive and pressure-sensitive adhesive sheet |
| CN1333804A (en) * | 1998-12-15 | 2002-01-30 | 艾弗里·丹尼森公司 | Removable emulsion pressure-sensitive adhesives |
| EP1318180A1 (en) * | 2001-12-06 | 2003-06-11 | Permacel | Aqueous pressure-sensitive adhesive composition, production method therefor and pressure-sensitive adhesive tape using the composition |
| CN100999650A (en) * | 2006-01-13 | 2007-07-18 | 日东电工株式会社 | Aqueous pressure-sensitive adhesive composition, pressure-sensitive adhesive tape and wire harness |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104021728A (en) * | 2014-06-24 | 2014-09-03 | 成都市天星印务有限公司 | Novel material formula of high-strength adhesive and fragile paper label thereof |
| CN110582548A (en) * | 2017-03-13 | 2019-12-17 | 陶氏环球技术有限责任公司 | Water-based pressure-sensitive adhesive composition and method for producing the same |
| CN108611026A (en) * | 2018-04-28 | 2018-10-02 | 王锦云 | A kind of aqueous EVA adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| US20140120338A1 (en) | 2014-05-01 |
| EP2636713B1 (en) | 2016-12-07 |
| US9163165B2 (en) | 2015-10-20 |
| CN103305145B (en) | 2015-11-18 |
| EP2636713A1 (en) | 2013-09-11 |
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